CN105190950A - Method of making a cathode - Google Patents

Method of making a cathode Download PDF

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Publication number
CN105190950A
CN105190950A CN201480017378.0A CN201480017378A CN105190950A CN 105190950 A CN105190950 A CN 105190950A CN 201480017378 A CN201480017378 A CN 201480017378A CN 105190950 A CN105190950 A CN 105190950A
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negative electrode
water
mixture
manganese dioxide
grams
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CN105190950B (en
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Y·G·阿瓦德
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Duracell US Operations Inc
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Gillette Co LLC
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0411—Methods of deposition of the material by extrusion
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/75—Wires, rods or strips
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/06—Electrodes for primary cells
    • H01M4/08—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/78—Shapes other than plane or cylindrical, e.g. helical
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture
    • Y10T29/49002—Electrical device making
    • Y10T29/49108—Electric battery cell making

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Primary Cells (AREA)

Abstract

A battery cathode is made by mixing electrochemically active cathode material, graphite, water and an aqueous based binder to provide a mixture. The mixture is extruded continuously into a cathode. Water is then removed from the cathode. The cathode is cut into individual pieces.

Description

Prepare the method for negative electrode
Technical field
The present invention relates to the method preparing storage battery negative electrode, and relate more specifically to the method for the preparation of storage battery.
Background technology
Electrochemical cell or storage battery are typically used as energy source.The negative electrode of the so-called anode of battery and the positive electrode of so-called negative electrode.Anode contains active material that can be oxidized; Negative electrode comprises or consumes the active material that can be reduced.Anode active material can reduce cathode active material.Spacer body is arranged between the anode and cathode.These assemblies are arranged in metal can.
When using storage battery as energy source in device, anode and negative electrode generation electrical contact, make electronics flow through device, and allow the respective oxidation of generation and reduction reaction to provide electric energy.And the electrolyte of anode and cathode contacts contains the ion of the spacer body flow through between electrode, to keep the charge balance of storage battery entirety at interdischarge interval.
Need to improve the method for the preparation of negative electrode.A kind of typical cathode preparation method is that negative electrode is pressed into pellet.Then by stacking for a series of pellet and insert in tank to form negative electrode.This technology needs multiple preparation process.
Carried out the trial of extruding negative electrode before.But these attempt needing there is the support of additional structure to provide the negative electrode with required integrality in extrusion, for being assembled into battery further.
Summary of the invention
The present invention relates to the method preparing storage battery negative electrode.The method comprises hybrid electrochemical active cathode material, graphite, water and water-based adhesive to provide the step of mixture.Mixture is extruded formation negative electrode continuously.Water is removed from negative electrode.Negative electrode is cut into single negative electrode.
The present invention relates to the method preparing storage battery.The method comprises the following steps: prepare negative electrode by hybrid electrochemical active cathode material, graphite, water and water-based adhesive to provide mixture.Mixture is extruded formation negative electrode continuously.Water is removed from negative electrode.Negative electrode is cut into single negative electrode.Negative electrode is inserted in tank.Spacer body is inserted in tank.Collector is inserted in tank.Anode is inserted in tank.Electrolyte is inserted in tank.Tank is sealed.
Accompanying drawing explanation
One or more embodiments of the detail of the present invention are set forth in accompanying drawing and following explanation.From the visible further feature of the present invention of this specification, accompanying drawing and claims, object and advantage.
Fig. 1 illustrates the method prepared for negative electrode.
Fig. 2 illustrates the plastogram of mixture to be extruded.
Fig. 3 illustrates the cross sectional configuration of negative electrode.
Fig. 4 illustrates the method prepared for storage battery.
Embodiment
Referring now to Fig. 1, it illustrates the method prepared for negative electrode.The method in blend step 150 hybrid electrochemical active cathode material 110, graphite 120, water 130 and aqueous binder 140 to form mixture 155.Then mixture 155 is extruded 160 formation negative electrodes 165 continuously.Water 170 is removed from negative electrode 165.Cut 180 negative electrodes 165 to form single negative electrode or sheet 185.
Electrochemical Iy active cathode material 110, graphite 120, water 130 and aqueous binder 140 inserted mixing arrangement and mix to form mixture.Aqueous binder 140 can be solution form or powder type.
Electrochemical Iy active cathode material 110 can comprise Mn oxide, manganese dioxide, electrolytic manganese dioxide (EMD), chemical manganese bioxide (CMD), high power electrolytic manganese dioxide (HPEMD), λ manganese dioxide and their mixture.Other electrochemical Iy active cathode material includes but not limited to silver oxide, nickel oxide, hydroxy nickel oxide, cupric oxide, bismuth oxide, high chemical valence nickel, their alloy and their mixture.Nickel oxide can comprise hydroxy nickel oxide, the hydroxy nickel oxide of hydroxy cobalt oxide coating, the laminated Li-Ni oxide of de-lithium and their combination.Hydroxy nickel oxide can comprise the commensal of beta-hydroxy nickel oxide, gamma-hydroxy nickel oxide and/or beta-hydroxy nickel oxide and/or gamma-hydroxy nickel oxide.The hydroxy nickel oxide of hydroxy cobalt oxide coating can comprise the beta-hydroxy nickel oxide of hydroxy cobalt oxide coating, the gamma-hydroxy nickel oxide of hydroxy cobalt oxide coating, and/or the commensal of the hydroxy cobalt oxide coating of beta-hydroxy nickel oxide and gamma-hydroxy nickel oxide.Nickel oxide can comprise and has chemical general formula Li 1-xh yni0 2part take off the stratiform nickel oxide of lithium, wherein 0.1<x<0.9 and 0.1<y<0.9.High chemical valence nickel can such as comprise tetravalence nickel.
Preferred electrochemical Iy active cathode material 110 is manganese dioxide, and it has the purity at least about 91 % by weight.Due to electrolytic manganese dioxide (EMD), there is high density and can obtain with high-purity with electrolytic method easily, so the electrolytic manganese dioxide preferred manganese dioxide form that is electrochemical cell.Chemical manganese bioxide (CMD) is a kind of manganese dioxide of chemical synthesis, has also been used as the electrochemical Iy active cathode material comprised in the electrochemical cell of alkaline battery and heavy battery.
EMD is manufactured by the Direct Electrolysis of the bath of manganese sulfate and sulfuric acid usually.The manufacture method of EMD and character thereof are found in the Batteries that KarlV.Kordesch edits, MarcelDekker, Inc. (NewYork), the 1st volume (1974), the 433 to 488 page.CMD usually by methods known in the art as prepared by " Sedema method ", the method is a kind of chemical method, is disclosed in United States Patent (USP) 2,956, in 860 (Welsh).LITHIUM BATTERY MnO 2can prepare via Sedema method, the method is by using MnSO 4with alkali metal chlorate (preferred NaClO 3) reactant mixture carry out.The dealer of manganese dioxide comprises Tronox, Erachem, Tosoh, DeltaManganese and Xiangtan.
Requiring low-down cell deformation or do not having in the storage battery of cell deformation, high power (HP) EMD can used.Preferably, high power electrolytic manganese dioxide has the open circuit voltage (OCV) of at least 1.635.Suitable high power electrolytic manganese dioxide can be commercially available from Tronox with trade name HighDrain.
Comprise graphite in the cathode and flow through negative electrode to allow electronics.Expanded graphite and native graphite can be used.In negative electrode, the amount of graphite is preferably relatively low, such as, be less than 8%, or even less than 6%, such as 2% to 5%.Lower content of graphite can comprise the active material of high level in negative electrode, battery volume can not be increased or reduce voidage (when must to hold it on certain level or certain level to prevent from producing gas in battery, internal pressure rises so high).Suitable expanded graphite can be obtained from such as Timcal.Other suitable graphite comprises Graphene and nanofiber graphite.
In general, preferably negative electrode is substantially free of unexpansive graphite.Although unexpansive graphite granule provides lubrification for negative electrode former, this kind of graphite is more much smaller than the conductivity of expanded graphite, therefore will obtain same cathodic conductivity and must use more amount.Although be not preferred, negative electrode can comprise the unexpansive graphite of low content, but this obtains being unfavorable for the graphite concentration reduced while keeping particular cathode conductivity.
Preferably, the water yield in mixture is in the scope of 10% to 20%.The water yield can be changed be easy to extrude to make mixture.
Aqueous binder 140 will be stable under electrochemical Iy active cathode material 110 exists.Aqueous binder 140 will have minimum swelling behavior in water.Minimum swelling behavior in water minimizes the volume of the negative electrode extruded, and provides relatively fine and close negative electrode.In addition, the swelling quantity minimizing aqueous binder 140 maximizes the amount of the electrochemical Iy active cathode material 110 in negative electrode.A kind of preferred aqueous binder 140 is hydroxypropyl methylcellulose (HPMC).Other aqueous binder 140 comprises polyacrylate and PVOH.Preferably, adhesive has and is no more than about 10% in water, no more than about 5%, be most preferably no more than about 3% swelling.
The amount of the aqueous binder in negative electrode is preferably relatively low, such as, be less than 3%, be preferably less than 2%, and preferably 0.2% to 2%, more preferably 0.4% to 1.2%.Lower aqueous binder agent content makes the active material that can comprise high level in negative electrode.
Mixture also can comprise other additive.The example of other cathode additive is described in such as United States Patent (USP) 5,698,315,5,919,598 and 5,997,775 and U.S. Patent application 10/765, in 569.Mixture also can comprise other material.Under these additional materials exist, the cementitiousness of adhesive should not affect adversely or suppress.Such as negative electrode can comprise electrolyte components such as potassium hydroxide.If comprise potassium hydroxide in negative electrode, so concentration of potassium hydroxide should be no more than 7%, otherwise adhesive will lose its cementitiousness.Adhesive is insoluble to the potassium hydroxide that concentration is less than 7%.Negative electrode also can comprise surfactant.Surfactant by compatible with adhesive for needs not cause adverse effect to cementitiousness.The example of suitable surfactant includes but not limited to anion surfactant, amphoteric surfactant and their combination.
A non-limiting example of suitable surfactant can comprise diphenyl sulfonate or derivatives thereof.In one embodiment, surfactant comprises the derivative that anion diphenyl sulfonate surfactant or its alkyl replace, and wherein hydrocarbyl group comprises 1 to about 24, preferably 1 to about 12 carbon atom.Concrete example comprises alkali metal alkyl diphenyl base oxidation disulfonate such as hexyl diphenyl oxidation sodium disulfonate, decyl diphenyl oxidation sodium disulfonate, dodecyl diphenyloxide disulfonic acid, dodecyl diphenyloxide sodium disulfonate, N-decyl diphenyl oxidation disulfonate, n-decyl diphenyl oxidation sodium disulfonate and n-cetyl diphenyl oxidation sodium disulfonate.Diphenyl sulfonate surfactant can be commercially available with general commodity name " Dowfax " from Dow, and specifically comprise DowfaxC6L, C10L, 2AO, 2A1,2A1-D, 2EP, 3BO, 3B2,3B2-D, 2000,8390 and 8390-D.
The example of anion surfactant is the stable alkali-soluble surfactant of chlorine bleaching.In one embodiment, anion surfactant is insoluble to the KOH higher than 5%, or is insoluble to the KOH of 30%.
Suitable diphenyl sulfonate surfactant can have formula as follows, and wherein R leaving group can be different.The example of different leaving groups comprises: DowfaxC6L has R=linear hexyl (C6); DowFax3B2 has R=straight chain decyl C10); DowFaxC10L has R=straight chain decyl (C10), comparatively highly sulfonated; DowFax2A1 has R=straight chain dodecyl (C12); And DowFax8390 has R=straight chain cetyl (C16).
Another non-limiting example of suitable surfactant comprises amphoteric surfactant.As used herein, term " both sexes " refers to and shows cation proterties at a low ph and the compound showing anion proterties at a high ph.Under the middle pH being called isoelectric point, compound is not only positively charged but also electronegative, that is, it is dipole ion.In one embodiment, amphoteric surfactant used herein dissolves in the KOH solution of 30%, but in this solution, show micro-surface activity to nothing.
In one example, amphoteric surfactant has following general formula:
Wherein R=C16, C12 or 2-ethylhexyl.The non-limiting example of the amphoteric surfactant of commercially available acquisition comprises: AmphotericLH, Amphoteric16, Amphoteric12 and Amphoteric400, all can be commercially available from AirProducts.
Negative electrode also can comprise the combination of other polymer and adhesive.
Before extrusion, the characteristic of negative electrode can be limited.Mixture can be placed in BrabenderPlastographECPlusN50Kneader torque rheometer and mediate with 25rpm.Kneader jacket temperature remains constant 20C.Referring now to Fig. 2, it illustrates the plastogram of cathode mix before extrusion.Plastic deformation illustrates cathode mix and has at least one peak, and its scope, at 20N-m to 200N-m, occurs between 1 second and 10 seconds.Cathode mix also can have the second peak after occurring in first peak, and has the peak scope of 20N-m to 140N-m.
Mixture 155 is extruded continuously 160 formation negative electrodes 165.Extruder can be the extruder of singe screw, twin-screw or other type.Extruder can be furnished with vacuum chamber outward with to mixture degasification, contributes to before mixture discharges extruding machine mold, make it fine and close.The porosity of the negative electrode 165 extruded regulates by retaining air, reduction extrusion pressure, the more water of interpolation and other method.
Water 170 is removed from negative electrode 165.Make a return journey by heated cathode in dryer and dewater.Negative electrode in dryer, can heat at the temperature between about 30 DEG C and 500 DEG C.Preferably, from negative electrode, the water of at least 50 % by weight is removed by heating.
Cut 180 negative electrodes 165 to form single negative electrode or sheet 185.Can before removal water, to remove after water or more the two cutting negative electrode 165.Before removal water, negative electrode 165 can be cut into the first length, and be cut to final lengths after removing water.
The ratio of electrochemical Iy active cathode material 110 pairs of graphite 120 is in the scope of 99:1 to 90:10.The ratio of electrochemical Iy active cathode material 110 and graphite 120 pairs of aqueous binders 140 is in the scope of 99.5:0.5 to 97:3.The ratio of electrochemical Iy active cathode material 110, graphite 120 and aqueous binder 140 pairs of water 130 is in the scope of 89:10.5 to 80:20.
The amount of the electrochemical Iy active cathode material in negative electrode can be described as negative electrode carrying capacity.Negative electrode carrying capacity can change according to the electrochemical Iy active cathode material used in storage battery and battery size.The negative electrode carrying capacity of at least 10.0 grams of manganese dioxide such as can be had with the AA storage battery of manganese bioxide electrochemical active cathode material.Negative electrode carrying capacity can be such as at least about 10.5 grams of manganese dioxide.Negative electrode carrying capacity can be such as between about 10.7 grams and about 11.5 grams of manganese dioxide.Negative electrode carrying capacity can be about 10.7 grams to about 11.0 grams manganese dioxide.Negative electrode carrying capacity can be about 10.8 grams to about 11.2 grams manganese dioxide.Negative electrode carrying capacity can be about 10.9 grams to about 11.5 grams manganese dioxide.For AAA storage battery, negative electrode carrying capacity can be about 4.0 grams to about 6.0 grams manganese dioxide.For AAAA storage battery, negative electrode carrying capacity can be about 2.0 grams to about 3.0 grams manganese dioxide.For C storage battery, negative electrode carrying capacity can be about 25.0 grams to about 29.0 grams manganese dioxide.For D storage battery, negative electrode carrying capacity can be about 54.0 grams to about 70.0 grams manganese dioxide.
The negative electrode extruded will have enough dry densities can have good conductivity.Cathode stem density is preferably between about 2.0g/cm 2and 3.5g/cm 2between, more preferably between about 2.4g/cm 2and between 3.3g/cm2.
Negative electrode will have enough integralities to bear the operation grasping and insert in tank.Negative electrode integrality can be defined by cathode stem bending strength.Cathode stem bending strength is preferably at least about 0.5N/mm 2, more preferably at least about 1.0N/mm 2and most preferably at least about 1.5N/mm 2.
It is desirable that negative electrode is being extruded contraction relatively minimum for experience between drying.The amount of linear cathode shrinkage is preferably and is less than about 5.0%.The amount of cross section cathode shrinkage is preferably and is less than about 5.0%.
Referring now to Fig. 3, which show negative electrode cross sectional configuration.Extruder can be equipped with suitable mould with preparation negative electrode cross sectional configuration as shown in Figure 3.Shown cross sectional configuration comprises circle, semicircle, star, multiple-blade shape, crescent, cheese, part annular and annular distance shape.
It is hereafter the example of negative electrode prepared in accordance with the present invention.
example 1
In the jacketed Sigma-cutter double arm kneading mixer of 40 liters, add 19.2kgEMD, add 0.8kg graphite subsequently.The binder solution of the SE-TyloseMOB20000P1 of 3445g3% is added in these powder.Open kneader, and whole one hour of composite material, maintain the temperature at 20 DEG C simultaneously.Resulting materials is placed in the KP80A type plunger-type extruder manufactured by ECT (Germany).Material is extruded by mould, and this mould has the external diameter of 14.5mm and the internal diameter of 8.45mm.Plunger-type extruder runs with the velocity of plunger in 10 to 50cm/min scope, and this speed corresponds to the extruding pipe velocity interval within the scope of 5-28m/min.Extruding pipe comprises the water of adhesive by dried ingredients weighing scale 0.52% and 14 % by weight.
example 2
In the jacketed Sigma-cutter double arm kneading mixer of 40 liters, add 20kg powder.This powder packets contains the graphite of 8 % by weight, remaining as EMD.The binder solution of the SE-TyloseMOB20000P1 of 4355g2.4% is added in these powder.Open kneader, and whole one hour of composite material, maintain the temperature at 20 DEG C simultaneously.The enterprising row relax of 80mm single screw extrusion machine that manufactured by Haendle (Germany) of resulting materials subsequently.Material is extruded by mould, and this mould has the external diameter of 13.2mm and the internal diameter of 7.7mm.Screw rod runs under the speed of about 5 to 34rpm, and this speed corresponds to 750g-6245g/min and corresponds to the pipe speed within the scope of 3-24.6m/min.The negative electrode extruded comprises the water of adhesive by dried ingredients weighing scale 0.6% and 13.75 % by weight.
Mixture can stand a conditioning step before being extruded formation negative electrode.Mixture can through conditioning, with by forming extrusioning mixture before negative electrode and increase fine and close thing and/or density being extruded by mixture.
Referring now to Fig. 4, it illustrates the method prepared for storage battery.In order to prepare negative electrode, the method merges electrochemical Iy active cathode material 110, graphite 120, water 130 and aqueous binder 140 to form mixture 155 in blend step 150.Then mixture 155 is extruded 160 formation negative electrodes 165 continuously.Water 170 is removed from negative electrode 165.Cut 180 negative electrodes 165 to form single negative electrode 185.
Electrochemical Iy active cathode material 110, graphite 120, water 130 and aqueous binder 140 are inserted in mixing arrangement and also mix to form mixture.Aqueous binder 140 can be solution form or powder type.
Electrochemical Iy active cathode material 110 can comprise Mn oxide, manganese dioxide, electrolytic manganese dioxide (EMD), chemical manganese bioxide (CMD), high power electrolytic manganese dioxide (HPEMD), λ manganese dioxide and their mixture.Other electrochemical Iy active cathode material includes but not limited to silver oxide, nickel oxide, hydroxy nickel oxide, cupric oxide, bismuth oxide, high chemical valence nickel, their alloy and their mixture.Nickel oxide can comprise hydroxy nickel oxide, the hydroxy nickel oxide of hydroxy cobalt oxide coating, the laminated Li-Ni oxide of de-lithium and their combination.Hydroxy nickel oxide can comprise the commensal of beta-hydroxy nickel oxide, gamma-hydroxy nickel oxide and/or beta-hydroxy nickel oxide and/or gamma-hydroxy nickel oxide.The hydroxy nickel oxide of hydroxy cobalt oxide coating can comprise the beta-hydroxy nickel oxide of hydroxy cobalt oxide coating, the gamma-hydroxy nickel oxide of hydroxy cobalt oxide coating, and/or the commensal of the hydroxy cobalt oxide coating of beta-hydroxy nickel oxide and gamma-hydroxy nickel oxide.Nickel oxide can comprise and has chemical general formula Li 1-xh yni0 2part take off the stratiform nickel oxide of lithium, wherein 0.1<x<0.9 and 0.1<y<0.9.High chemical valence nickel can such as comprise tetravalence nickel.
Preferred electrochemical Iy active cathode material 110 is manganese dioxide, and it has the purity at least about 91 % by weight.Due to electrolytic manganese dioxide (EMD), there is high density and can obtain with high-purity conveniently by electrolytic method, so electrolytic manganese dioxide (EMD) the preferred manganese dioxide form that is electrochemical cell.Chemical manganese bioxide (CMD) is a kind of manganese dioxide of chemical synthesis, has also been used as the electrochemical Iy active cathode material comprised in the electrochemical cell of alkaline battery and heavy battery.
EMD is manufactured by the Direct Electrolysis of the bath of manganese sulfate and sulfuric acid usually.The Batteries that KarlV.Kordesch edits is found in, MarcelDekker, Inc. (NewYork), the 1st volume (1974), the 433 to 488 page for the manufacture of the method for EMD and character thereof.CMD usually by methods known in the art as prepared by " Sedema method ", the method is a kind of chemical method, is disclosed in United States Patent (USP) 2,956, in 860 (Welsh).LITHIUM BATTERY MnO 2can prepare via Sedema method, the method is by using MnSO 4with alkali metal chlorate (preferred NaClO 3) reactant mixture carry out.The dealer of manganese dioxide comprises Tronox, Erachem, Tosoh, DeltaManganese and Xiangtan.
Requiring low-down cell deformation or do not having in the storage battery of cell deformation, high power (HP) EMD can used.Preferably, HPEMD has the open circuit voltage (OCV) of at least 1.635.Suitable HPEMD can be commercially available from Tronox with trade name HighDrain.
Comprise graphite in the cathode and flow through negative electrode to allow electronics.Expanded graphite and native graphite can be used.In negative electrode, the amount of graphite is preferably relatively low, such as, be less than 8%, or even less than 6%, such as 2% to 5%.Lower content of graphite can comprise the active material of high level in negative electrode, the volume of battery can not be increased or reduce voidage (when must to hold it on certain level or certain level to prevent from producing gas in battery, internal pressure is too high).Suitable expanded graphite can be obtained from such as Timcal.Other suitable graphite comprises Graphene and nanofiber graphite.
In general, preferably negative electrode is substantially free of unexpansive graphite.Although unexpansive graphite granule provides lubrification for negative electrode former, this kind of graphite is more much smaller than the conductivity of expanded graphite, therefore will obtain same cathodic conductivity and must use more amount.Although be not preferred, negative electrode can comprise the unexpansive graphite of low content, but this obtains being unfavorable for the graphite concentration reduced while keeping particular cathode conductivity.
Preferably, in mixture, the amount of water is in the scope of 10% to 20%.The amount that can change water is easy to extrude to make mixture.
Aqueous binder 140 will be stable under electrochemical Iy active cathode material 110 exists.Aqueous binder 140 will have minimum swelling behavior in water.Minimum swelling behavior in water minimizes the volume of the negative electrode extruded, thus provides relatively fine and close negative electrode.In addition, the swelling quantity minimizing aqueous binder 140 maximises the amount of the electrochemical Iy active cathode material 110 in negative electrode.A kind of preferred aqueous binder 140 is hydroxypropyl methylcellulose (HPMC).Other aqueous binder 140 comprises polyacrylate and PVOH.
The amount of the aqueous binder in negative electrode is preferably relatively low, such as, be less than 3%, be preferably less than 2%, and preferably 0.2% to 2%, more preferably 0.4% to 1.2%.Lower aqueous binder agent content makes the active material that can comprise high level in negative electrode.
Mixture also can comprise other additive.The example of other cathode additive is described in such as United States Patent (USP) 5,698,315,5,919,598 and 5,997,775 and U.S. Patent application 10/765, in 569.Mixture also can comprise other material.Under these additional materials exist, the cementitiousness of adhesive should not affect adversely or suppress.Such as negative electrode can comprise electrolyte components such as potassium hydroxide.If comprise potassium hydroxide in negative electrode, so concentration of potassium hydroxide should be no more than 7%, otherwise adhesive will lose its cementitiousness.Adhesive is insoluble to the potassium hydroxide that concentration is less than 7%.Negative electrode also can comprise surfactant.Surfactant by compatible with adhesive for needs not cause adverse effect to cementitiousness.The example of suitable surfactant includes but not limited to anion surfactant, amphoteric surfactant and their combination.
A non-limiting example of suitable surfactant can comprise diphenyl sulfonate or derivatives thereof.In one embodiment, surfactant comprises the derivative that anion diphenyl sulfonate surfactant or its alkyl replace, and wherein hydrocarbyl group comprises 1 to about 24, preferably 1 to about 12 carbon atom.Concrete example comprises alkali metal alkyl diphenyl base oxidation disulfonate as hexyl diphenyl oxidation sodium disulfonate, decyl diphenyl oxidation sodium disulfonate, dodecyl diphenyloxide disulfonic acid, dodecyl diphenyloxide sodium disulfonate, N-decyl diphenyl oxidation disulfonate, n-decyl diphenyl oxidation sodium disulfonate and n-cetyl diphenyl oxidation sodium disulfonate.Diphenyl sulfonate surfactant can be commercially available with general commodity name " Dowfax " from Dow, and specifically comprise DowfaxC6L, C10L, 2AO, 2A1,2A1-D, 2EP, 3BO, 3B2,3B2-D, 2000,8390 and 8390-D.
The example of anion surfactant is the stable alkali-soluble surfactant of chlorine bleaching.In one embodiment, anion surfactant is insoluble to the KOH higher than 5%, or is insoluble to the KOH of 30%.
Suitable diphenyl sulfonate surfactant can have general formula as follows, and wherein R leaving group can be different.The example of different leaving group comprises: DowfaxC6L has R=linear hexyl (C6); DowFax3B2 has R=straight chain decyl C10); DowFaxC10L has R=straight chain decyl (C10), comparatively highly sulfonated; DowFax2A1 has R=straight chain dodecyl (C12); And DowFax8390 has R=straight chain cetyl (C16).
Another non-limiting example of suitable surfactant comprises amphoteric surfactant.As used herein, term " both sexes " refers to and shows cation proterties at a low ph and the compound showing anion proterties at a high ph.Under the middle pH being called isoelectric point, compound is not only positively charged but also electronegative, that is, it is dipole ion.In one embodiment, amphoteric surfactant used herein dissolves in the KOH solution of 30%, but in this solution, show micro-surface activity to nothing.
In one example, amphoteric surfactant has following general formula:
Wherein R=C16, C12 or 2-ethylhexyl.The non-limiting example of the amphoteric surfactant of commercially available acquisition comprises: AmphotericLH, Amphoteric16, Amphoteric12 and Amphoteric400, and it all can be commercially available from AirProducts.
Negative electrode also can comprise the combination of other polymer and adhesive.
Mixture 155 is extruded continuously 160 formation negative electrodes 165.Extruder can be the extruder of singe screw, twin-screw or other type.Extruder can be furnished with vacuum chamber outward with to mixture degasification, thus contributes to discharging before extruding machine mold at mixture making it fine and close.The porosity of the negative electrode 165 extruded regulates by retaining air, reduction extrusion pressure, the more water of interpolation and other method.
Water 170 is removed from negative electrode 165.Water is removed by heated cathode.That heating can be conduction or convection current or their combination.Preferably, negative electrode heats in dryer.Negative electrode in dryer, can heat at the temperature between 30 DEG C and 500 DEG C.Preferably, from negative electrode, remove the water of at least 50 % by weight.Include but not limited to that evaporation and distillation remove water from negative electrode by other technology.
Cut 180 negative electrodes 165 to form single negative electrode 185.Cutting negative electrode 165 can occur in remove before water, remove water after or more the two all have.Before removal water, negative electrode 165 can be cut into the first length, and be cut to final lengths after removing water.
The ratio of electrochemical Iy active cathode material 110 pairs of graphite 120 is in the scope of 99:1 to 90:10.The ratio of electrochemical Iy active cathode material 110 and graphite 120 pairs of aqueous binders 140 is in the scope of 99.5:0.5 to 97:3.The ratio of electrochemical Iy active cathode material 110, graphite 120 and aqueous binder 140 pairs of water 130 is in the scope of 89:10.5 to 80:20.
The amount of the electrochemical Iy active cathode material in negative electrode can be described as negative electrode carrying capacity.Negative electrode carrying capacity can change according to the electrochemical Iy active cathode material used in storage battery and battery size.The negative electrode carrying capacity of at least 10.0 grams of manganese dioxide such as can be had with the AA storage battery of manganese bioxide electrochemical active cathode material.Negative electrode carrying capacity can be such as at least about 10.5 grams of manganese dioxide.Negative electrode carrying capacity can be such as between about 10.7 grams and about 11.5 grams of manganese dioxide.Negative electrode carrying capacity can be about 10.7 grams to about 11.0 grams manganese dioxide.Negative electrode carrying capacity can be about 10.8 grams to about 11.2 grams manganese dioxide.Negative electrode carrying capacity can be about 10.9 grams to about 11.5 grams manganese dioxide.For AAA storage battery, negative electrode carrying capacity can be about 4.0 grams to about 6.0 grams manganese dioxide.For AAAA storage battery, negative electrode carrying capacity can be about 2.0 grams to about 3.0 grams manganese dioxide.For C storage battery, negative electrode carrying capacity can be about 25.0 grams to about 29.0 grams manganese dioxide.For D storage battery, negative electrode carrying capacity can be about 54.0 grams to about 70.0 grams manganese dioxide.
The negative electrode extruded will have enough dry densities can have good conductivity.Cathode stem density is preferably between about 2.0g/cm 2and 3.5g/cm 2between, more preferably between about 2.4g/cm 2and between 3.3g/cm2.
Negative electrode will have enough integralities to bear the operation grasping and insert in tank.Negative electrode integrality defines by cathode stem bending strength.Cathode stem bending strength is preferably at least about 0.5N/mm 2, more preferably at least about 1.0N/mm 2and most preferably at least about 1.5N/mm 2.
It is desirable that negative electrode is being extruded contraction relatively minimum for experience between drying.The amount of linear cathode shrinkage is preferably and is less than about 5.0%.The amount of cross section cathode shrinkage is preferably and is less than about 5.0%.
Negative electrode can have any one in cross sectional configuration as shown in Figure 3.
Negative electrode 185 is inserted in tank 200.Tank can be made up of the material of any general type being generally used for primary alkali storage battery, and can be made up of any suitable material such as such as nickel-plated cold-rolled or plastics.Tank preferably includes seal.Seal can be made up of such as polyamide (nylon).Tank can have conventional cylinder shape – or can have any other suitable non-cylindrical shape, such as prism shape.The inwall of tank can by material processed electrode to low electrical contact resistance.The inwall of tank can be electroplated, and such as, with nickel, cobalt plating, or scribbles carbon and carries paint.
Spacer body is inserted in tank 210.Spacer body can comprise to be weaved or non-woven paper wood or fabric.Spacer body can comprise the cellophane layer be such as combined with non-woven material layer.Spacer body also can comprise additional non-woven material layer.Separator material can be thin material.Such as spacer body can have the dry thickness being less than 150 microns (microns).Such as spacer body can have the dry thickness being less than 100 microns.Spacer body preferably has about 70 microns to about 90 microns, more preferably the dry thickness of about 70 microns to about 75 microns.Spacer body has 40g/m 2or less basic weight.Spacer body preferably has about 15g/m 2to about 40g/m 2, also more preferably about 20g/m 2to about 30g/m 2basic weight.
Spacer body is inserted in tank 220.Collector can be made of metal, such as zinc, copper, brass, bronze or other suitable material any.Collector is optionally electroplated with tin, zinc, bismuth, indium or another kind of suitable material, and this material is at collector and such as have low electrical contact resistance between anode.
Anode is inserted in tank 230.Anode can be formed by least one electro-chemical activity anode material, gelling agent and trace mineral supplement such as gassing inhibitors.Electro-chemical activity anode material can comprise zinc; Calcium; Iron; Metal hydride is AB such as 5, AB 2, and A 2b 7; Their alloy; And their mixture.
The amount of the electro-chemical activity anode material in anode can be described as anode carrying capacity.Anode carrying capacity can change according to the electro-chemical activity anode material used in storage battery and battery size.Such as, the AA storage battery with zinc electro-chemical activity anode material can have the anode carrying capacity at least about 3.3 grams of zinc.Anode carrying capacity can be such as at least about 4.0, about 4.3, about 4.6 grams, about 5.0 grams, or about 5.5 grams of zinc.Such as, the AAA storage battery with zinc electro-chemical activity anode material can have the anode carrying capacity at least about 1.9 grams of zinc.Such as anode carrying capacity can have at least about 2.0 or about 2.1 grams of zinc.Such as, the AAAA storage battery with zinc electro-chemical activity anode material can have the anode carrying capacity at least about 0.6 gram of zinc.Such as anode carrying capacity can have at least about 0.7 to about 1.0 gram of zinc.Such as, the C storage battery with zinc electro-chemical activity anode material can have the anode carrying capacity at least about 9.5 grams of zinc.Such as anode carrying capacity can have at least about 10.0 to about 15.0 grams of zinc.Such as, the D storage battery with zinc electro-chemical activity anode material can have the anode carrying capacity at least about 19.5 grams of zinc.Such as anode carrying capacity can have at least about 20.0 to about 30.0 grams of zinc.
The example of spendable gelling agent comprises polyacrylic acid, grafted starch material, polyacrylic salt, carboxymethyl cellulose, the salt (such as sodium carboxymethylcellulose) of carboxymethyl cellulose or their combination.Anode can comprise gassing inhibitors, and it can comprise inorganic material, such as bismuth, tin or indium.Alternatively, gassing inhibitors can include organic compounds, such as phosphate, ionic surface active agent or non-ionic surface active agent.
Electrolyte is inserted in tank 240.Electrolyte dispersibles in whole negative electrode, anode and spacer body.Electrolyte comprises the ionic conductivity component in the aqueous solution.Ionic conductivity component can be hydroxide.Hydroxide can be such as NaOH, potassium hydroxide, lithium hydroxide, cesium hydroxide and their mixture.Ionic conductivity component also can comprise salt.Salt can be such as zinc chloride, ammonium chloride, magnesium perchlorate, magnesium bromide and their mixture.The concentration of ionic conductivity component can be selected according to the performance of battery designs and expectation thereof.A kind of aqueous alkaline electrolyte can comprise hydroxide aqueous solution as ionic conductivity component.The concentration of the hydroxide in electrolyte can be about 0.25 to about 0.35 with electrolytical total weight, or about 25% to about 35%.Such as, the hydroxide concentration in electrolyte can be about 0.25 to about 0.32 with electrolytical total weight, or about 25% to about 32%.
The concentration of ionic conductivity component measures by collecting alkaline battery such as the electrolytical total amount in AA or AAA alkaline cell assembled.This generally realizes by removing spacer body, negative electrode and anode assemblies and being dissolved in hydrochloric acid solution by these assemblies.Hydrogen peroxide dropwise can be added contribute to course of dissolution.Then can by the solution dilution of dissolving to designated volume to provide analyte.Then can via inductively coupled plasma (ICP) emission spectrometer, such as JYUltratrace or its equivalent, analyze described analyte, with the total cation concentration of the ionic conductivity component in determination and analysis thing, such as potassium (K+) concentration (ppm).The total cation concentration measured from analyte via ICP is used in the cation total weight in the electrolyte solution mathematically determining the alkaline battery sampled, such as in gram potassium (K+), and determine the weight of ionic conductivity component subsequently, such as in gram potassium hydroxide (KOH).Electrolytical ionic conductivity component is as the concentration based on electrolyte weight of potassium hydroxide (KOH), and the total weight by ionic conductivity component measures divided by analyte weight.
Aqueous alkaline electrolyte also can comprise zinc oxide (ZnO).ZnO can be used for suppressing the zine corrosion in anode.The concentration of the ZnO comprised in electrolyte can be and is less than about 3% by electrolyte weight.Such as ZnO concentration can be and is less than about 2% by electrolyte weight.
Such as, in AA alkaline battery, the electrolytical total weight of aqueous alkaline can be about 3.0 grams to about 4.0 grams.Such as, the weight of AA storage battery Inner electrolysis matter preferably can be about 3.3 grams to about 3.8 grams.Such as, the weight of AA storage battery Inner electrolysis matter more preferably can be about 3.4 grams to about 3.6 grams.Such as, in AAA alkaline battery, the electrolytical total weight of aqueous alkaline can be about 1.0 grams to about 2.0 grams.Such as, the weight of AAA storage battery Inner electrolysis matter preferably can be about 1.2 grams to about 1.8 grams.Such as, the weight of AA storage battery Inner electrolysis matter more preferably can be about 1.4 grams to about 1.6 grams.
By tank sealing 250.
Should understand, dimension disclosed herein and value are not intended to be strictly limited to quoted exact value.On the contrary, except as otherwise noted, each such dimension is intended to the scope that represents described value and be functionally equal to around this value.Such as, the dimension being disclosed as " 40mm " is intended to represent " about 40mm ".
Limit unless expressly excluded, or otherwise, by the every section of document quoted, comprise any cross reference or Patents or patent application herein, be incorporated herein by reference in full.Quoting of any document is not to its prior art as disclosed herein or claimed any invention; its individually or with any combination of other list of references any, or with reference to, propose, suggestion or disclose any accreditation that this type of is invented.In addition, when any implication of same term in any implication of term in the present invention or definition and the file that is incorporated to way of reference or when defining contradiction, the implication or definition of giving this term in the present invention should be obeyed.
Although illustrate and described specific embodiment of the present invention, it is obvious to those skilled in the art that can make multiple other without departing from the spirit and scope of the present invention changes and modification.Therefore, be intended to contain in claims all these belonging in the scope of the invention herein change and modification.

Claims (15)

1. prepare a method for storage battery negative electrode, described method comprises:
Hybrid electrochemical active cathode material, graphite, water and water-based adhesive are to provide mixture;
Described mixture is extruded formation negative electrode continuously;
Water is removed from described negative electrode; And
Described negative electrode is cut into single negative electrode.
2. method according to claim 1, wherein removes described water by the described negative electrode of heating.
3., according to method in any one of the preceding claims wherein, wherein remove described water by heating described negative electrode between about 20 DEG C and 500 DEG C.
4., according to method in any one of the preceding claims wherein, from described negative electrode, wherein removed the described water of at least 50 % by weight by heating.
5., according to method in any one of the preceding claims wherein, wherein said electrochemical Iy active cathode material is selected from Mn oxide, manganese dioxide, electrolytic manganese dioxide (EMD), chemical manganese bioxide (CMD), high power electrolytic manganese dioxide (HPEMD), λ manganese dioxide and their mixture.
6., according to method in any one of the preceding claims wherein, wherein said water-based adhesive comprises hydroxypropyl methylcellulose.
7. according to method in any one of the preceding claims wherein, wherein said negative electrode is extruded with at least two longitudinal slices, and their combinations are to form the equivalent that a longitudinal direction extrudes negative electrode.
8., according to method in any one of the preceding claims wherein, wherein said adhesive is insoluble to the potassium hydroxide that concentration is less than 7%.
9. according to method in any one of the preceding claims wherein, wherein said negative electrode also comprises surfactant.
10., according to method in any one of the preceding claims wherein, wherein said adhesive has in the water being no more than 10% swelling.
11. according to method in any one of the preceding claims wherein, and wherein said negative electrode has the linear cathode shrinkage being less than 5.0%.
12. according to method in any one of the preceding claims wherein, and wherein said negative electrode has the cross section cathode shrinkage being less than 5.0%.
13. according to method in any one of the preceding claims wherein, and wherein said mixture has at least one peak from 20N-m to 200N-m at the time place between 1 second and 10 seconds.
14. according to method in any one of the preceding claims wherein, and described method also comprises conditioning step, wherein before described mixture being extruded formation negative electrode, extrudes described mixture.
15. according to method in any one of the preceding claims wherein, and wherein said negative electrode has at least 0.5N/mm 2dry bending strength.
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